EP1230289B1 - Procede de preparation de polyols a mousse souple en bloc - Google Patents

Procede de preparation de polyols a mousse souple en bloc Download PDF

Info

Publication number
EP1230289B1
EP1230289B1 EP00964106A EP00964106A EP1230289B1 EP 1230289 B1 EP1230289 B1 EP 1230289B1 EP 00964106 A EP00964106 A EP 00964106A EP 00964106 A EP00964106 A EP 00964106A EP 1230289 B1 EP1230289 B1 EP 1230289B1
Authority
EP
European Patent Office
Prior art keywords
ethylene oxide
mixture
carbon atoms
oxide
molecule
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Revoked
Application number
EP00964106A
Other languages
German (de)
English (en)
Other versions
EP1230289A1 (fr
Inventor
Georg Heinrich Grosch
Harald Larbig
Reinhard Lorenz
Dieter Junge
Kathrin Harre
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=7922469&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP1230289(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by BASF SE filed Critical BASF SE
Publication of EP1230289A1 publication Critical patent/EP1230289A1/fr
Application granted granted Critical
Publication of EP1230289B1 publication Critical patent/EP1230289B1/fr
Anticipated expiration legal-status Critical
Revoked legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4866—Polyethers having a low unsaturation value
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
    • C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
    • C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0008—Foam properties flexible
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0041—Foam properties having specified density
    • C08G2110/005—< 50kg/m3

Definitions

  • the invention relates to a process for the preparation of polyether alcohols, the polyether alcohols produced by this process as well as their use for the production of polyurethanes.
  • Polyether alcohols are used in large quantities for the production of Polyurethanes used. They are usually manufactured by catalytic addition of lower alkylene oxides, in particular Ethylene oxide and propylene oxide, on H-functional starter substances. Basic metal hydroxides or are usually used as catalysts Salts are used, with the potassium hydroxide being the most practical Has meaning.
  • the alkylene oxides are usually added as a block or as a statistical mixture. With block-by-block attachment only one alkylene oxide is added at the same time, in the statistical Mixture contains a mixture of alkylene oxides the reaction mixture.
  • multimetal cyanide complex compounds mostly zinc hexacyanometalates, also as DMC catalysts referred to for the production of polyether alcohols known with low levels of unsaturated components. It are a large number of documents in which the manufacture describes such compounds. So in DD-A-203 735 and DD-A-203 734 the production of polyetherols using of zinc hexacyanocobaltate is described.
  • Polyether alcohols used in the manufacture of flexible flexible foams are usually used directly on the starting substance a full propylene oxide inner block that can hold up to 40% by weight of the total polyol, and on this Propylene oxide inner block mixing blocks made of propylene oxide and ethylene oxide, which are at least 60% by weight of the total polyol and contain at least 2% by weight of ethylene oxide.
  • These polyols are usually produced using basic catalysis.
  • WO-A-97 / 27,236 describes the production of a flexible flexible foam polyol, where at least the propylene oxide inner block under Use of multimetal cyanides as a catalyst becomes. With this method, however, there is a further increase the content of ethylene oxide in the polyether alcohol without the above described disadvantages not possible.
  • the object of the invention was to develop polyether alcohols which have a high content of ethylene oxide without it significant increase in the hydrophilicity of the products comes.
  • a polyether alcohol which can be prepared by ring-opening polymerization of ethylene oxide and alkylene oxides with at least 3 carbon atoms, an inner block of ethylene oxide or one Mixture of ethylene oxide and alkylene oxides with at least Contains 3 carbon atoms, and then at least one alkylene oxide with at least 3 carbon atoms, or a mixture of Ethylene oxide and alkylene oxides with at least 3 carbon atoms, preferably propylene oxide, the mixing blocks preferably at least 2% by weight and at most 20% by weight Ethylene oxide, based on the mixture.
  • the invention accordingly relates to polyether alcohols, can be produced by ring-opening polymerization of ethylene oxide and Propylene oxide on H-functional starter substances, characterized in that that a maximum of 40 wt .-%, based on the starting substance the weight of the polyether alcohol, ethylene oxide or a mixture from ethylene oxide and alkylene oxides with at least 3 carbon atoms, with an ethylene oxide content of at least 98% by weight, based on the mixture, is deposited and thereafter at least an alkylene oxide having at least 3 carbon atoms, or a Mixture of ethylene oxide and at least one alkylene oxide at least 3 carbon atoms, with a maximum content 20 wt .-% ethylene oxide, based on the mixture, is added and at least one multimetal cyanide compound as catalyst is used.
  • ethylene oxide content is at least 0.5% by weight, based on the mixture.
  • alkylene oxides with at least 3 carbon atoms in the molecule come preferably propylene oxide, butylene oxide and iso-butylene oxide and any mixtures of at least two of the above Alkylene oxides, particularly preferably propylene oxide, are used.
  • the polyether alcohol at the chain end that is after the Addition of the alkylene oxides with at least 3 carbon atoms or the mixture of ethylene oxide and alkylene oxides with at least 3 carbon atoms, still ethylene oxide attached become.
  • the amount of this at the chain end is preferably accumulated ethylene oxide maximum 15 wt .-%, based on the Weight of the polyether alcohol.
  • Such polyether alcohols preferably for the production of cold-molded polyurethane foams used.
  • Polyether alcohols according to the invention without this end block from ethylene oxide are preferably used for the production of Flexible polyurethane foams, in particular block flexible foams, are used.
  • the invention further relates to a method for Preparation of the polyether alcohols described above.
  • the production The polyether alcohols according to the invention are carried out by ring opening polymerization of the alkylene oxides ethylene oxide and Alkylene oxides with at least 3 carbon atoms on H-functional Starting substances in the presence of catalysts, as described in claim 6.
  • Processes are used as catalysts for the addition of Alkylene oxides multimetal cyanides, often also as DMC catalysts designated, used.
  • DMC catalysts are due to the higher reaction rate in the addition of the alkylene oxides, on the other hand the polyether alcohols thus produced have a lower Content of unsaturated constituents.
  • this embodiment is that when using DMC catalysts to delay the start of the reaction on Reaction start can come.
  • the invention also relates to polyurethanes that can be produced by reacting polyisocyanates with compounds containing at least two hydrogen atoms reactive with isocyanate groups, characterized in that as compounds with at least two with isocyanate-reactive hydrogen atoms the invention Polyether alcohols are used.
  • the invention Polyether alcohols are preferred for the production of Polyurethane flexible foams are used, the polyether alcohols without a terminal ethylene oxide block, especially for production of block foams and thermoformed foams and the Polyether alcohols with a terminal ethylene oxide block in particular be used for the production of cold molded foams.
  • Polyetherols become the multifunctional ones known for this Alcohols with 2 to 8 hydroxyl groups in the molecule.
  • polyether alcohols like them usually for the production of flexible polyurethane foams be used, 2- and / or 3-functional alcohols, for example Ethylene glycol, propylene glycol, glycerin, trimethylolpropane, for use.
  • the polyether alcohols according to the invention preferably have a Molecular weight in the range of 1000 to 100,000.
  • alkylene oxides include ethylene oxide and Alkylene oxides with at least 3 carbon atoms, in the already mentioned proportions for use.
  • These compounds are prepared according to generally known methods Process by making the aqueous solution of a water soluble Metal salt with the aqueous solution of a hexacyanometalate compound, especially a salt or an acid, united and one during or after the union water-soluble ligands.
  • the multimetal cyanide compounds are suitable because of their high activity excellent for the synthesis of the invention Polyether.
  • the catalyst concentrations used are less than 1% by weight, preferably less than 0.5% by weight, particularly preferably less than 1000 ppm, in particular less than 500 ppm, particularly preferably less than 100 ppm based on the total mass of produced polyether polyol.
  • the production of polyether alcohols by means of the multimetal cyanide compounds both take place continuously or discontinuously.
  • the synthesis can in suspension, fixed bed, fluid bed or floating bed mode respectively.
  • the Accumulation of the alkylene oxides occurs at temperatures between 50 ° C and 200 ° C, with temperatures between 90 ° C and 150 ° C preferred and pressures in the range of 0.001 bar and 100 bar
  • the reaction vessel usually by purging with an inert gas, for example nitrogen.
  • alkylene oxides usually follows a post-reaction phase to complete sales of the To effect alkylene oxides.
  • the resulting polyether alcohol is like usually worked up by initially unreacted alkylene oxide and other volatile components by stripping or Distillation and, if necessary, suspended matter and / or mechanical impurities by filtration from the raw polyether alcohol be removed.
  • the catalyst can be removed from the polyether alcohol as usual.
  • the basic catalyst is usually used with a Acid neutralizes and the resulting salts by filtration removed from the polyether alcohol.
  • the catalyst can in principle Polyether alcohol can remain, if necessary, it can also be removed, for example by filtration.
  • the polyether alcohols according to the invention are outstandingly suitable for the production of polyurethanes, in particular flexible polyurethane foams. They are very good with the other ingredients of the polyurethane formulations are compatible and, despite their comparatively high content of ethylene oxide units in the polyether chain, little hydrophilic. Because of the higher reaction speed the polymerization of ethylene oxide in comparison to propylene oxide is the space-time yield in production the polyether alcohols of the invention higher than in conventional polyether alcohols for the same areas of application. A further increase in the space-time yield can be achieved if at least part of the alkylene oxides by means of multimetal cyanide compounds is deposited as a catalyst.
  • the resulting polyether alcohol had the following characteristics: Hydroxyl number: 394 mgKOH / g, viscosity at 25 ° C: 240 mPa * s, Potassium content: 5 ppm.
  • the resulting polyether alcohol had the following characteristics: Hydroxyl number: 219 mg KOH / g, viscosity at 25 ° C: 222 mPa * s, Potassium content: 3 ppm.
  • the syntheses were carried out in a 10 l stirred reactor.
  • the reaction products from Examples 1 and 2 were introduced at 50 ° C.
  • the reactor contents were rendered inert by evacuation three times and then filling with nitrogen.
  • the degassing was carried out by evacuating for 1.5 hours at 105 ° C. and a pressure of less than 1 mbar abs.
  • a double metal cyanide catalyst from the reaction of zinc acetate with cobalt hexacyanoic acid and tert-butanol was added. It was again evacuated three times and filled with nitrogen. This was followed by an approximately half-hour evacuation of temperature increase to 125 ° C, with an evacuation to a pressure less than 1 mbar abs. on.
  • Table 1 shows polyether alcohols.
  • All polyether alcohols have an inner block made of glycerin and Ethylene oxide. In example 3, this is followed by a mixing block from ethylene oxide and propylene oxide, in Example 4 follows Propylene oxide block.
  • Polyether alcohols were obtained which have only a small proportion of unsaturated constituents. Products with a very low hydroxyl number can be obtained by the process according to the invention. The molecular weight distributions of the polyether alcohols are narrow in all cases.
  • the polyol and isocyanate components shown in Table 2 in Comparative Example 5 and Example 6 converted to flexible polyurethane foams.
  • the components of the Polyol components were mixed intensively. After that, the isocyanate added with stirring and the reaction mixture in potted an open mold, making it into polyurethane foam ausDuumte.
  • Example 5 Example 6 polyol Hydroxyl number [mgKOH / g] Amount [g] Amount [g] Polyol A 48 1000 Polyol from Example 4 48 1000 water 6233 38 38 BF 2370 10 10 Amine catalyst N 201 560 1.9 1.9 Amine catalyst N 206 426 0.6 0.6 Tin catalyst K 29 0 2.3 2.5 total 1053 1,053.0 isocyanate NCO [%] Amount [g] Amount [g] TDI 80/20 48.3 488.0 488.0 index 110 110 test data unit start time [S] 15 10 setting time [S] 90 80 Rise time [S] 90 85 rising height [Mm] 275 265 Rise height after 5 min [Mm] 270 260 Air permeability [MmWs] 10 10 density [Kg / m3] 25.3 26.4 Compression hardness at 40% [KPa

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyethers (AREA)
  • Polyurethanes Or Polyureas (AREA)

Claims (9)

  1. Polyétheralcools, pouvant être préparés par polymérisation avec ouverture de cycle, d'oxyde d'éthylène et d'au moins un oxyde d'alkylène ayant au moins trois atomes de carbone dans la molécule, sur des substances de départ à fonctionnalité H, caractérisés en ce que l'on fixe par addition de l'oxyde d'éthylène ou un mélange d'oxyde d'éthylène et d'au moins un oxyde d'alkylène ayant au moins trois atomes de carbone dans la molécule, avec une teneur en oxyde d'éthylène d'au moins 98% en poids, par rapport au mélange, à chaque fois en une quantité de 40% en poids au maximum par rapport au poids du polyétheralcool, sur la substance de départ, puis on y fixe par addition au moins un oxyde d'alkylène ayant au moins trois atomes de carbone dans la molécule ou un mélange d'oxyde d'éthylène et d'au moins un oxyde d'alkylène ayant au moins trois atomes de carbone dans la molécule, avec une teneur de 20% en poids au maximum d'oxyde d'éthylène par rapport au mélange et on met en oeuvre au moins un composé cyanure multimétallique en tant que catalyseur.
  2. Polyéthéralcools selon la revendication 1, caractérisés en ce que l'oxyde de propylène, l'oxyde de butylène, l'oxyde d'isobutylène, ou des mélanges quelconques d'au moins deux des oxydes d'alkylène cités, sont mis en oeuvre en tant qu'oxydes d'alkylène ayant au moins trois atomes de carbone dans la molécule.
  3. Polyétheralcools selon la revendication 1, caractérisés en ce que l'oxyde de propylène est mis en oeuvre en tant qu'oxyde d'alkylène ayant au moins trois atomes de carbone dans la molécule.
  4. Polyétheralcools selon la revendication 1, caractérisés en ce que l'oxyde d'éthylène est fixé par addition à l'extrémité de la chaíne.
  5. Polyétheralcools selon la revendication 4, caractérisés en ce que 15% en poids au maximum d'oxyde d'éthylène par rapport au poids du polyétheralcool sont fixés par addition à l'extrémité de la chaíne.
  6. Procédé de préparation de polyétheralcools par polymérisation avec ouverture de cycle, d'oxyde d'éthylène et d'au moins un oxyde d'alkylène ayant au moins trois atomes de carbone dans la molécule sur des substances de départ à fonctionnalité H, caractérisé en ce que l'on fixe par addition de l'oxyde d'éthylène ou un mélange d'oxyde d'éthylène et d'au moins un oxyde d'alkylène ayant au moins trois atomes de carbone dans la molécule avec une teneur en oxyde d'éthylène d'au moins 98% en poids par rapport au mélange à chaque fois en une quantité de 40% en poids au maximum par rapport au poids du polyétheralcoôl, sur la substance de départ puis on y fixe par addition au moins un oxyde d'alkylène ayant au moins trois atomes de carbone dans la molécule ou un mélange d'oxyde d'éthylène et d'au moins un oxyde d'alkylène ayant au moins trois atomes de carbone dans la molécule avec une teneur en oxyde d'éthylène de 20% en poids au maximum par rapport au mélange, et on met en oeuvre au moins un composé cyanure multimétallique en tant que catalyseur.
  7. Procédé selon la revendication 6, caractérisé en ce que l'on met en oeuvre au moins un composé basique en tant que catalyseur, pour l'addition de l'oxyde d'éthylène ou du mélange d'oxyde d'éthylène et d'au moins un oxyde d'alkylène, ayant au moins trois atomes de carbone dans la molécule avec une teneur en oxyde d'éthylène d'au moins 98% en poids, par rapport au mélange, et on met en oeuvre au moins un composé cyanure multimétallique en tant que catalyseur pour l'addition d'au moins un oxyde d'alkylène ayant au moins trois atomes de carbone dans la molécule ou du mélange d'oxyde d'éthylène et d'au moins un oxyde d'alkylène ayant au moins trois atomes de carbone dans la molécule avec une teneur de 20% en poids au maximum d'oxyde d'éthylène, par rapport au mélange.
  8. Procédé de préparation de polyétheralcools selon la revendication 4, caractérisé en que l'on met en oeuvre au moins un composé basique en tant que catalyseur pour l'addition d'oxyde d'éthylène ou du mélange d'oxyde d'éthylène et d'au moins un oxyde d'alkylène ayant au moins trois atomes de carbone dans la molécule avec une teneur en oxyde d'éthylène d'au moins 98% en poids par rapport au mélange, sur la substance de départ et on met en oeuvre au moins un composé cyanure multimétallique en tant que catalyseur pour l'addition du au moins un oxyde d'alkylène ayant au moins trois atomes de carbone dans la molécule ou du mélange d'oxyde d'éthylène et d'au moins un oxyde d'alkyléne ayant au moins trois atomes de carbone dans la molécule avec une teneur en oxyde d'éthylène de 20% en poids au maximum, par rapport au mélange et on met en oeuvre au moins un composé basique en tant que catalyseur pour l'addition de l'oxyde d'éthylène sur l'extrémité de la chaíne.
  9. Polyuréthanes, pouvant être préparés par réaction de polyisocyanates avec des composés ayant au moins deux atomes d'hydrogène réagissant avec des groupes isocyanates, caractérisés en ce que des polyétheralcools selon l'une quelconque des revendications 1 à 5 sont mis en oeuvre en tant que composés ayant au moins deux atomes d'hydrogène réagissant avec des groupes isocyanates.
EP00964106A 1999-09-17 2000-09-05 Procede de preparation de polyols a mousse souple en bloc Revoked EP1230289B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19944762 1999-09-17
DE19944762A DE19944762A1 (de) 1999-09-17 1999-09-17 Verfahren zur Herstellung von Blockweichschaumpolyolen
PCT/EP2000/008640 WO2001021682A1 (fr) 1999-09-17 2000-09-05 Procede de preparation de polyols a mousse souple en bloc

Publications (2)

Publication Number Publication Date
EP1230289A1 EP1230289A1 (fr) 2002-08-14
EP1230289B1 true EP1230289B1 (fr) 2004-12-08

Family

ID=7922469

Family Applications (1)

Application Number Title Priority Date Filing Date
EP00964106A Revoked EP1230289B1 (fr) 1999-09-17 2000-09-05 Procede de preparation de polyols a mousse souple en bloc

Country Status (17)

Country Link
EP (1) EP1230289B1 (fr)
JP (1) JP2003510384A (fr)
CN (1) CN1180003C (fr)
AR (1) AR025579A1 (fr)
AT (1) ATE284427T1 (fr)
AU (1) AU7514400A (fr)
BR (1) BR0014055A (fr)
CA (1) CA2385085A1 (fr)
CZ (1) CZ2002838A3 (fr)
DE (2) DE19944762A1 (fr)
ES (1) ES2233443T3 (fr)
HU (1) HUP0202600A3 (fr)
MX (1) MXPA02002471A (fr)
PL (1) PL203194B1 (fr)
PT (1) PT1230289E (fr)
RU (1) RU2257394C2 (fr)
WO (1) WO2001021682A1 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW200516093A (en) 2003-09-19 2005-05-16 Asahi Glass Co Ltd Flexible polyurethane foam and process for producing the same
US9284401B2 (en) 2006-11-13 2016-03-15 Bayer Materialscience Llc Process for the preparation of polyether-ester polyols
ZA200709673B (en) * 2006-11-13 2009-09-30 Bayer Materialscience Ag Process for the preparation of polyether-ester polyols
KR101223841B1 (ko) * 2007-12-19 2013-01-17 바스프 에스이 폴리에테르 알콜의 제조 방법
KR101797265B1 (ko) 2010-08-24 2017-11-13 다우 글로벌 테크놀로지스 엘엘씨 에틸렌 옥시드/프로필렌 옥시드 폴리에테르 폴리올 및 그로부터 제조된 폴리우레탄
US20180186921A1 (en) * 2015-07-02 2018-07-05 Shell Oil Company Improvements relating to polyurethanes

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4008189A (en) * 1974-06-03 1977-02-15 Olin Corporation Hydrophilic polyurethane foam
US4487854A (en) * 1983-12-27 1984-12-11 Basf Wyandotte Corporation Polyoxyalkylene polyether polyols and polyurethane foams prepared therefrom
DE3531212A1 (de) * 1985-08-31 1987-03-05 Henkel Kgaa Als entschaeumer verwendbare alkylenoxid-blockpolymere
US5122548A (en) * 1990-03-23 1992-06-16 The Dow Chemical Company Elastomeric polyisocyanate-based polymers from polyoxyalkylene polyols containing internal polyoxyethylene blocks
JPH07128793A (ja) * 1993-11-05 1995-05-19 Konica Corp 染料の固体微粒子分散物および該分散物を含有するハロゲン化銀写真感光材料
US5563221A (en) * 1995-06-21 1996-10-08 Arco Chemical Technology, L.P. Process for making ethylene oxide-capped polyols from double metal cyanide-catalyzed polyols

Also Published As

Publication number Publication date
MXPA02002471A (es) 2002-07-30
HUP0202600A2 (hu) 2002-12-28
PT1230289E (pt) 2005-04-29
AU7514400A (en) 2001-04-24
BR0014055A (pt) 2002-05-21
ES2233443T3 (es) 2005-06-16
RU2257394C2 (ru) 2005-07-27
PL354042A1 (en) 2003-12-15
CN1374977A (zh) 2002-10-16
CA2385085A1 (fr) 2001-03-29
DE19944762A1 (de) 2001-03-22
CZ2002838A3 (cs) 2002-08-14
CN1180003C (zh) 2004-12-15
HUP0202600A3 (en) 2004-05-28
JP2003510384A (ja) 2003-03-18
PL203194B1 (pl) 2009-09-30
DE50008921D1 (de) 2005-01-13
WO2001021682A1 (fr) 2001-03-29
AR025579A1 (es) 2002-12-04
EP1230289A1 (fr) 2002-08-14
ATE284427T1 (de) 2004-12-15

Similar Documents

Publication Publication Date Title
EP1021453B1 (fr) Complexes cyanures a metaux multiples s&#39;utilisant comme catalyseurs
EP1071509B1 (fr) Catalyseurs cyanures dimetalliques perfectionnes pour la preparation de polyols de polyether
EP1206498B1 (fr) Procede de preparation de polyetherpolyols
EP1115490B1 (fr) Catalyseurs a base de cyanure bimetallique pour la preparation de polyols de polyether
EP1100617B1 (fr) Catalyseurs de cyanure bimetallique utilises pour preparer des polyols de polyether
EP1208132B1 (fr) Alcools de polyether
WO2001053381A1 (fr) Procede pour la production d&#39;alcools de polyether
EP1230289B1 (fr) Procede de preparation de polyols a mousse souple en bloc
EP1115489B1 (fr) Catalyseurs a base de cyanure bimetallique pour la preparation de polyols de polyether
EP1165659B1 (fr) Procede de preparation de polyetherpolyols
EP1175454B1 (fr) Procede de preparation de polyurethanes
DE10226415A1 (de) Verfahren zur Herstellung von Polyetheralkoholen
EP1117723B2 (fr) Procede de production de polyetherols par polymerisation par ouverture de chaine d&#39;oxydes d&#39;alkylene
WO2004029131A1 (fr) Procede de production d&#39;alcools de polyether
DE10210125A1 (de) Verfahren zur Herstellung von hochfunktionellen Polyetheralkoholen
EP1423454A1 (fr) Procede de production de mousses souples de polyurethanne
DE19809538A1 (de) Verfahren zur Herstellung von Doppelmetallcyanidkatalysatoren

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20020222

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

AX Request for extension of the european patent

Free format text: AL;LT;LV;MK;RO;SI

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20041208

Ref country code: IE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20041208

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: GERMAN

REF Corresponds to:

Ref document number: 50008921

Country of ref document: DE

Date of ref document: 20050113

Kind code of ref document: P

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 20050202

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20050308

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20050308

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20050308

REG Reference to a national code

Ref country code: PT

Ref legal event code: SC4A

Free format text: AVAILABILITY OF NATIONAL TRANSLATION

Effective date: 20050302

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2233443

Country of ref document: ES

Kind code of ref document: T3

REG Reference to a national code

Ref country code: IE

Ref legal event code: FD4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20050905

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20050905

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20050930

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20050930

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20050930

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20050930

26 Opposition filed

Opponent name: THE DOW CHEMICAL COMPANY

Effective date: 20050907

PLAX Notice of opposition and request to file observation + time limit sent

Free format text: ORIGINAL CODE: EPIDOSNOBS2

ET Fr: translation filed
NLR1 Nl: opposition has been filed with the epo

Opponent name: THE DOW CHEMICAL COMPANY

PLAF Information modified related to communication of a notice of opposition and request to file observations + time limit

Free format text: ORIGINAL CODE: EPIDOSCOBS2

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PLBB Reply of patent proprietor to notice(s) of opposition received

Free format text: ORIGINAL CODE: EPIDOSNOBS3

PLCK Communication despatched that opposition was rejected

Free format text: ORIGINAL CODE: EPIDOSNREJ1

APAH Appeal reference modified

Free format text: ORIGINAL CODE: EPIDOSCREFNO

APBP Date of receipt of notice of appeal recorded

Free format text: ORIGINAL CODE: EPIDOSNNOA2O

RAP2 Party data changed (patent owner data changed or rights of a patent transferred)

Owner name: BASF SE

APBQ Date of receipt of statement of grounds of appeal recorded

Free format text: ORIGINAL CODE: EPIDOSNNOA3O

NLT2 Nl: modifications (of names), taken from the european patent patent bulletin

Owner name: BASF SE

Effective date: 20080305

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: PT

Payment date: 20080825

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20080915

Year of fee payment: 9

Ref country code: IT

Payment date: 20080926

Year of fee payment: 9

Ref country code: NL

Payment date: 20080903

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20080910

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20080919

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20080922

Year of fee payment: 9

Ref country code: ES

Payment date: 20081021

Year of fee payment: 9

APBU Appeal procedure closed

Free format text: ORIGINAL CODE: EPIDOSNNOA9O

RDAF Communication despatched that patent is revoked

Free format text: ORIGINAL CODE: EPIDOSNREV1

PLAO Information deleted related to despatch of communication that opposition is rejected

Free format text: ORIGINAL CODE: EPIDOSDREJ1

RDAG Patent revoked

Free format text: ORIGINAL CODE: 0009271

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: PATENT REVOKED

27W Patent revoked

Effective date: 20090614

GBPR Gb: patent revoked under art. 102 of the ep convention designating the uk as contracting state

Effective date: 20090614

REG Reference to a national code

Ref country code: PT

Ref legal event code: MP4A

Effective date: 20091020

NLR2 Nl: decision of opposition

Effective date: 20090614